CN WAD FS3000 A002966 OIA1677 FS 3k - Updated

Method OIA-1677: Available Cyanide
Methodology
Method OIA-1677: Available Cyanide by

Ligand Exchange and Flow Injection Analysis (FIA)
(Cartridge Part #A001982 or #A002654)
1.0 Scope and Application
1.1 This method is used for the determination of available cyanide in water and wastewater by ligand
exchange, flow injection analysis, and amperometric detection according to USEP A Method
OIA-1677 (References 15.3, 15.4, 15.9, and 15.10). This method is used in the USEP A’s data
gathering and monitoring programs associated with the Clean Water Act, Resource Conservation
and Recovery Act, Comprehensive Environmental Response, Compensation and Liability Act,
and Safe Drinking Water Act.
1.2 Cyanide ion (CN –), hydrogen cyanide in water (HCN(aq)), and the cyano-complexes of zinc,
copper, cadmium, mercury, nickel, and silver may be determined by this method. The presence of
polysulfides and colloidal material may prove intractable for application of this method.
1.3 The Method Detection Limit (MDL) of this method is 0.5 µg/L cyanide (Reference 15.9). The
applicable range of the method is 2.0 µg/L (ppb) to 5.0 mg/L (ppm) cyanide using a 200-µL
sample loop. The range may be extended to analyze higher concentrations by sample dilution or
changing the volume of the sample loop.
2.0 Summary of Method
2.1 Prior to analysis, the sample is treated to remove potential interferences (Section 4.0 and 8.0).
Ligand exchange reagents are added to the sample. Thermodynamically stable complexes are
formed with the transition metal ions listed in Section 1.2, releasing the cyanide ion from the
cyano-complexes. An aliquot of the treated sample is injected into the Flow Injection Analysis
(FIA) system (Reference 15.1). The addition of hydrochloric acid converts the cyanide ion to
hydrogen cyanide gas (HCN), which passes under a gas diffusion membrane. The hydrogen
cyanide gas diffuses through the membrane into an alkaline receiving solution where it is con-
verted back to cyanide ion. The cyanide ion is monitored amperometrically with a silver working
electrode, silver/silver chloride reference electrode, and platinum/stainless steel counter electrode
at an applied potential of zero volt. The current generated is proportional to the cyanide concen-
tration present in the original sample.
2.2 The quality of the analysis is assured through reproducible calibration and testing of the Flow
Injection Analysis (FIA) system.
Part #A002966 CNSolution 3000

Publication 13590401
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2.3 A general flow diagram of the FIA system is shown below (see Section 17.0 for a detailed flow
diagram).
Gas
Diffusion
Module
Sodium
Hydroxide AMP To
Detector Waste
Sample
Carrier To
Waste
Hydrochloric
Acid
3.0 Definitions
Definitions for terms used in this method are provided in Section 16.0, “Glossary of Definitions and
Purposes.”
4.0 Interferences
4.1 Method interferences may be caused by contaminants in the reagents, reagent water , glassware,
etc., which may bias the results. Care should be taken to keep all such items free of contaminants.
4.2 Sulfide is a positive interferant in this method (Reference 15.11). When sulfide is acidified, it
forms hydrogen sulfide, which passes through the gas diffusion membrane and produces a signal
at the silver electrode. In addition, sulfide ion reacts with cyanide ion in solution to reduce its
concentration over time. Samples containing sulfide must be treated according to Section 8.4.
4.3 Sample containing water soluble aldehydes, such as formaldehyde or acetaldehyde, are treated by
adding ethylenediamine solution (Section 8.5).
4.4 Oxidizing agents that decompose cyanides are removed by adding ascorbic acid (Section 8.6)
4.5 High concentrations of carbonate may result in a negative response in the amperometric detector
when carbon dioxide diffuses across the gas diffusion membrane into the alkaline receiving
solution, reducing its pH. Effluents from high-carbonate containing wastes, such as coal gasifica-
tion waste and atmospheric emission scrub water , can be treated with hydrated lime to stabilize
the sample (Reference 15.11).
4.6 Tests conducted on samples containing lar ge amounts of colloids indicate rapid cyanide losses.
Filtration can be used to remove colloids, but measured cyanide levels may be adversely affected.

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5.0 Safety
5.1 The toxicity or carcinogenicity of each compound or reagent used in this method has not been
fully established. Each chemical should be treated as a potential health hazard. Exposure to these
chemicals should be reduced to the lowest possible level.
5.2 For reference purposes, a file of Material Safety Data Sheets (MSDS) for each chemical used in
this method should be available to all personnel involved in this chemical analysis. The prepara-
tion of a formal safety plan is also advisable.
5.3 The following chemicals used in this method may be highly toxic or hazardous and should be
handled with extreme caution at all times. Consult the appropriate MSDS before handling.
5.3.1 Acetic Acid, glacial, C 2H4O2 (FW 60.05)
5.3.2 Acetone, C3H6O (FW 58.08)
5.3.3 5-[4-(Dimethylamino)benzylidene]rhodanine, C12H12N2OS 2 (FW 264.37)
5.3.4 Ethylenediamine, anhydrous, C 2H8N2 (FW 60.10)
5.3.5 Mercury(II) Cyanide, Hg(CN) 2 (FW 252.63)
5.3.6 Nickel(II) Cyanide, Ni(CN) 2 (FW 110.73)
5.3.7 Potassium Cyanide, KCN (FW 65.12)
5.3.8 Silver Nitrate, AgNO3 (FW 169.88)
5.3.9 Sodium Acetate, anhydrous, C 2H3O2Na (FW 82.03)
5.3.10 Sodium Hydroxide, NaOH (FW 40.00)
5.3.11 WAD Cyanide Reagent A (Part #A001416)
5.3.12 WAD Cyanide Reagent B (Part #A001417)
5.4 Unknown samples may be potentially hazardous and should be handled with extreme caution at
all times.
5.5 Proper personal protective equipment (PPE) should be used when handling or working in the
presence of chemicals.
5.6 This method does not address all safety issues associated with its use. The laboratory is respon-
sible for maintaining a safe work environment and a current awareness file of OSHA regulations
regarding the safe handling of the chemicals specified in this method.

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6.0 Apparatus, Equipment, and Supplies
6.1 Flow Injection Analysis (FIA) System (OI Analytical CNSolution™ 3000) consisting of the
following:
6.1.1 120-Place Autosampler
6.1.2 Amperometric detection system with:
6.1.2.1 Silver working electrode
6.1.2.2 Silver/silver chloride reference electrode
6.1.2.3 Platinum/stainless steel counter electrode
6.1.2.4 Applied potential of zero volt
6.1.3 Data Acquisition System (PC or Notebook PC) with WinFLOW™ software
6.1.4 Available Cyanide, Method OIA-1677 Cartridge (Part #A001982 or #A002654)
6.2 Sampling equipment—Sample bottle, amber glass, with polytetrafluoroethylene (PTFE)-lined cap.
Clean by washing with deter gent and water, rinsing with two aliquots of reagent water , and drying
by baking at 1 10°–150°C for a minimum of one hour .
6.3 Standard laboratory equipment including volumetric flasks, pipettes, syringes, etc. should all be
cleaned, rinsed, and dried per bottle cleaning procedure in Section 6.2.
7.0 Reagents and Calibrants
7.1 Raw Materials
7.1.1 Acetic Acid, glacial, C 2H4O2 (FW 60.05)
7.1.2 Acetone, C3H6O (FW 58.08)
7.1.3 Ascorbic Acid, C6H8O6 (FW 176.12)
7.1.4 Deionized Water (ASTM Type I or II)
7.1.5 5-[4-(Dimethylamino)benzylidene]rhodanine, C12H12N2OS 2 (FW 264.37)
7.1.6 Ethylenediamine, anhydrous, C 2H8N2 (FW 60.10)
7.1.7 Mercury(II) Cyanide, Hg(CN) 2 (FW 252.63)
7.1.8 Nickel(II) Cyanide, Ni(CN) 2 (FW 110.73)

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7.1.9 Potassium Cyanide, KCN (FW 65.12)
7.1.10 Silver Nitrate, AgNO3 (FW 169.88)
7.1.11 Sodium Acetate, anhydrous, C 2H3O2Na (FW 82.03)
7.1.12 Sodium Hydroxide, NaOH (FW 40.00)
7.1.13 WAD Cyanide Reagent A (Part #A001416)
7.1.14 WAD Cyanide Reagent B (Part #A001417)
7.2 Reagent Preparation
Note: For best results, filter and degas all reagents prior to use.
7.2.1 Reagent Water
7.2.1.1 Degassed and deionized reagent water can be prepared in one of the following
manners:
7.2.1.1.1 Place distilled/deionized water under a strong vacuum for

15–20 minutes. Magnetic stirring or sonification will aid in the
degassing process.
7.2.1.1.2 Purge distilled/deionized water with a stream of nitrogen gas (or other
inert gas) through a glass frit for approximately 5 minutes.
7.2.1.1.3 Boil distilled/deionized water in an Erlenmeyer flask for 15–20 minutes.

Remove the flask from the heat source, cover it with an inverted beaker ,
and allow it to cool to room temperature.
7.2.1.2 After preparing the degassed reagent water , store the reagent water in a tightly
sealed container to protect it from reabsorption of atmospheric gases. For best
results, store degassed reagent water under a slight vacuum when not in use.
7.2.2 Sample Preservation Reagents
7.2.2.1 Acetate Buffer (1 L)
7.2.2.1.1 Dissolve 146 g of sodium acetate anhydrous in 400 mL of reagent

water (Section 7.2.1).
7.2.2.1.2 Add 480 g of glacial acetic acid. Dilute to 1,000 mL with reagent water
in a 1-L volumetric flask and mix well.
7.2.2.2 Ethylenediamine Solution, 3.5% v/v (100 mL)
7.2.2.2.1 Dilute 3.5 mL of ethylenediamine to 100 mL with reagent water in a

100-mL volumetric flask and mix well.

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7.2.2.3 Ascorbic Acid—Crystals
7.2.3 Quality Control Reagents
Warning: Cyanide ion, hydrocyanic acid, all cyanide salts, and most metal-
cyanide complexes are extremely dangerous. As a contact poison,
cyanide does not need to be ingested to produce toxicity . Also, cyanide
solutions produce fatally toxic hydrogen cyanide gas when acidified.
For these reasons, it is mandatory that work with cyanide be carried out
in a well-ventilated hood by properly trained personnel wearing ad-
equate protective equipment.
7.2.3.1 Sodium Hydroxide, 1 M (1 L)
7.2.3.1.1 While stirring, carefully add 40 g of sodium hydroxide in 700 mL of

reagent water in a 1-L volumetric flask.
7.2.3.1.2 Cool to room temperature. Dilute to 1,000 mL with reagent water and
mix well.
Warning: Mixing sodium hydroxide with water releases a great

amount of heat. Take appropriate precautions, such as
cooling the solution while adding the sodium hydroxide.
Note: Store in an amber bottle at room temperature.
7.2.3.2 Nickel(II) Cyanide Stock Solution, 1,000 mg/L Cyanide (100 mL)
7.2.3.2.1 Dissolve 0.213 g of nickel(II) cyanide in 25 mL of reagent water and

1 mL of 1 M sodium hydroxide (Section 7.2.3.1) in a
100-mL volumetric flask.
7.2.3.2.2 Dilute to 100 mL with reagent water and mix well.
7.2.3.3 Mercury(II) Cyanide Stock Solution, 1,000 mg/L Cyanide (100 mL)
7.2.3.3.1 Dissolve 0.486 g of mercury(II) cyanide in 25 mL of reagent water and

1 mL of 1 M sodium hydroxide in a 100-mL volumetric flask.
7.2.3.4 Nickel(II) Cyanide Working Solution, 2 mg/L Cyanide (100 mL)
7.2.3.4.1 Add 0.2 mL of nickel(II) cyanide stock solution (Section 7.2.3.2) to

25 mL of reagent water and 1 mL of 1 M sodium hydroxide (Section
7.2.3.1) in a 100-mL volumetric flask.

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7.2.3.5 Mercury(II) Cyanide Working Solution, 2 mg/L Cyanide (100 mL)
7.2.3.5.1 Add 0.2 mL of mercury(II) cyanide stock solution (Section 7.2.3.3) to

25 mL of reagent water and 1 mL of 1 M sodium hydroxide in a
100-mL volumetric flask.
7.2.4 FIA Reagents
7.2.4.1 Carrier and Hydrochloric Acid Solution (1 L)
7.2.4.1.1 Add 8 mL of concentrated hydrochloric acid to approximately 800 mL

of reagent water in a 1-L volumetric flask.
7.2.4.1.2 Dilute to 1,000 mL with reagent water and mix well.
Warning: Mixing hydrochloric acid with water releases a great

amount of heat. Take appropriate precautions.
7.2.4.2 Acceptor Stock Solution, 5 M Sodium Hydroxide (1 L)
7.2.4.2.1 While stirring, carefully add 200 g of sodium hydroxide in 700 mL of

reagent water in a 1-L volumetric flask.
7.2.4.2.2 Cool to room temperature. Dilute to 1,000 mL with reagent water and
mix well.

7.2.4.3 Acceptor Reagent, 0.1 M Sodium Hydroxide (1 L)
7.2.4.3.1 Dilute 20 mL of acceptor stock solution (Section 7.2.4.2) with reagent

water to 1,000 mL in a 1-L volumetric flask and mix well.
7.2.4.4 WAD Reagent A (Part #A001416)
Note: Store at 4°C. If stored properly , the WAD Reagent A is stable for ap-
proximately 6 months after opening.

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Note: After opening, check the WAD Reagent A monthly. Adjust a sample of
2 mg/L nickel(II) cyanide working solution (Section 7.2.3.4) to pH 12.
Treat the nickel(II) cyanide sample with the WAD Reagent A according
to Section 11.1 and proceed with the analysis to confirm the cyanide
recovery.
7.2.4.5 WAD Reagent B (Part #A001417)
Note: Store at 4°C. If stored properly , the WAD Reagent B is stable for ap-
proximately 6 months after opening.
Note: After opening, check the WAD Reagent B monthly . Adjust a sample of
2 mg/L mercury(II) cyanide working solution (Section 7.2.3.5) to
pH 12. Treat the mercury(II) cyanide sample with the WAD Reagent B
according to Section 11.1 and proceed with the analysis to confirm the
cyanide recovery.
7.3 Calibrant Preparation
Warning: Cyanide ion, hydrocyanic acid, all cyanide salts, and most metal-cyanide com-
plexes are extremely dangerous. As a contact poison, cyanide does not need to
be ingested to produce toxicity . Also, cyanide solutions produce fatally toxic
hydrogen cyanide gas when acidified. For these reasons, it is mandatory that
work with cyanide be carried out in a well-ventilated hood by properly trained
personnel wearing adequate protective equipment.
7.3.1 Stock Solutions
7.3.1.1 Silver Nitrate Solution, 0.0192 N (1 L)
7.3.1.1.1 Dissolve 3.27 g of silver nitrate in 700 mL of reagent water in a

1-L volumetric flask.
7.3.1.2 Rhodanine Solution, 0.2 mg/mL in Acetone (100 mL)
7.3.1.2.1 Dissolve 20 mg of 5-[4-(dimethylamino)benzylidene]rhodanine in

80 mL of acetone in a 100-mL volumetric flask.
7.3.1.2.2 Dilute to 100 mL with acetone and mix well.
7.3.1.3 Potassium Cyanide Stock Solution, 1,000 mg/mL (1 L)
7.3.1.3.1 Dissolve 2 g of sodium hydroxide in 500 mL of reagent water in a


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7.3.1.3.2 Add 2.51 g of potassium cyanide. Dilute to 1,000 mL with reagent

water and mix well.

Note: Store in an amber bottle at 4°C. If stored properly , this

reagent is typically stable for 2 months.
7.3.1.4 Standardized Potassium Cyanide Stock Solution
7.3.1.4.1 Add 0.5 mL of rhodanine solution (Section 7.3.1.2) to 25 mL of potas-

sium cyanide stock solution (Section 7.3.1.3).
7.3.1.4.2 Titrate with silver nitrate solution (Section 7.3.1.1) until the color
changes from canary yellow to a salmon hue.
7.3.1.4.3 Based on the determined potassium cyanide concentration, dilute the

potassium cyanide stock solution to the final concentration of 1.00 g/L
using Equation 1. If the concentration is not 1.00 g/L, correct the
intermediate and working calibration concentrations accordingly .

reagent is typically stable for 2 months
EQUATION 1
xV1 = CV2
Where:
x = Concentration of potassium cyanide stock solution determined from titrations
C = 1.00 g/L potassium cyanide
V1 = Volume (in L) of potassium cyanide stock solution needed to prepare 1 L of
1.00 g/L standardized potassium cyanide stock solution
V2 = 1 L, final volume (in L) of standardized potassium cyanide stock solution
7.3.2 Secondary Calibrants
7.3.2.1 Cyanide, 100 mg/L (1 L)
7.3.2.1.1 Add 100 mL of standardized potassium cyanide stock solution (Section

7.3.1.4) and 10 mL of 1 M sodium hydroxide (Section 7.2.3.1) to a

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reagent is typically stable for 2–4 weeks.
7.3.2.2 Cyanide, 10 mg/L (1 L)
7.3.2.2.1 Use a volumetric pipet to add 10 mL of standardized potassium cyanide

stock solution and 10 mL of 1 M sodium hydroxide to a 1-L volumetric
flask.

7.3.2.3 Cyanide, 1 mg/L (1 L)
7.3.2.3.1 Use a volumetric pipet to add 1 mL of standardized potassium cyanide

stock solution (Section 7.3.1.4) and 1 mL of 1 M sodium hydroxide
(Section 7.2.3.1) to a 1-L volumetric flask.

7.3.3 Working Calibrants
7.3.3.1 Add the designated volumes of secondary calibrant (see Equation 2) to the
required number of 100-mL volumetric flasks that each contain approximately
40 mL of reagent water .
7.3.3.2 Dilute each solution to the mark with reagent water and mix well.
Note: Prepare working calibrants fresh daily .

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EQUATION 2
C1 V 1 = C 2 V 2
Where:
C1 = Concentration (in mg/L) of stock solution (or calibrant)
V1 = Volume (in L) of stock solution (or calibrant) to be used
C2 = Desired concentration (in mg/L) of working calibrant to be prepared
V2 = Final volume (in L) of working calibrant to be prepared
By solving this equation for the volume of stock solution to be used ( V1), the following equation is
obtained:
V1 = C2V2
C1
Since the desired concentration ( C2), the final volume ( V2), and the concentration of the stock solution
(C1) are all known for any given calibrant concentration in a defined volume, the volume of stock
solution to be used ( V1) is easily calculated.
7.3.3.3 Calibrants covering the entire range of this analysis can be prepared from the
following table.
Volume of Secondary Calibrant Solution (mL)

Working Calibrant
Final Cyanide Cyanide Cyanide
Concentration 1 mg/L 10 mg/L 100 mg/L
(µg/L)
2.0 0.20
5.0 0.50 0.05
10 1.0 0.10
50 5.0 0.50 0.05
100 10 1.0 0.10
200 20 2.0 0.20
500 50 5.0 0.50
1,000 10 1.0
3,000 30 3.0
5,000 50 5.0

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8.0 Sample Collection, Preservation, and Storage
8.1 Samples should be collected in plastic or glass bottles that have been thoroughly cleaned and
rinsed with reagent water (Section 7.2.1).
8.2 The volume of sample collected should be sufficient to ensure that a representative sample is
obtained, replicate analysis is possible, and waste disposal is minimized.
8.3 Determine cyanide in unpreserved samples within 24 hours or as soon as possible to eliminate
loss of analyte.
8.4 Samples Containing Sulfide Ion
8.4.1 Precipitate sulfide ion with lead ion immediately upon sample collection. Sulfide ion and
lead sulfide will react with cyanide ion to form thiocyanate, which is not detected in the
analytical system. If lead carbonate is used for sulfide precipitation, the supernate contain-
ing cyanide must be filtered immediately to avoid loss of cyanide through reaction with
precipitated lead sulfide (Reference 15.11).
8.4.2 Test samples with lead acetate test paper to determine the presence or absence of sulfide
ion. Note that the lead acetate test paper can be unreliable and is typically not usable for
sulfide concentrations below approximately 1 ppm. If the presence of sulfide is suspected
but not verifiable by the lead acetate test paper , two samples may be collected—one
without lead carbonate addition and another with lead carbonate addition followed by
immediate filtration. Analyze both samples. If sulfide is present, the preserved sample
should contain higher levels of cyanide than the unpreserved sample. Lead acetate test
paper should be tested for minimum level of sulfide detection by spiking reagent water
aliquots with decreasing levels of sulfide. The spiked samples are tested with lead acetate
test paper moistened with acetate buffer (Section 7.2.2.1). Each new batch of test paper
and/or acetate buffer should be tested to determine the lowest level of sulfide ion detec-
tion prior to use.
8.5 Treat samples containing or suspected to contain formaldehyde, acetaldehyde, or other water
soluble aldehydes with 20 mL of 3.5% ethylenediamine solution (Section 7.2.2.2) per liter of
sample.
8.6 Treat samples containing chlorine, hypochlorite, and/or sulfite with 0.6 g of ascorbic acid per liter
of sample.
8.7 Treat samples containing high concentrations of carbonate with hydrated lime.
8.7.1 Slowly add hydrated lime while stirring to raise the pH of the sample to 12.0–12.5.
8.7.2 Decant the sample after the precipitate has settled.
8.8 The holding time for preserved samples is 14 days from the time of collection (Reference 15.8).
Sample analysis should be performed as soon as possible to eliminate loss of analyte.

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9.0 Quality Control
9.1 Each laboratory that uses this method is required to operate a formal quality assurance program
(Reference 15.6). The minimum requirements of this program consist of an initial demonstration
of laboratory capability and the periodic analysis of Laboratory Control Samples (LCSs) and
Matrix Spike/Matrix Spike Duplicates (MS/MSDs) as a continuing check on performance. Labora-
tory performance is compared to established performance criteria to determine if the results of the
analyses meet the performance characteristics of the method.
9.1.1 The analyst shall make an initial demonstration of the ability to generate acceptable
precision and accuracy with this method. This ability is established as described in
Section 9.2.
9.1.2 In recognition of advances that are occurring in analytical technology and to allow the
analyst to overcome sample matrix interferences, the analyst is permitted certain options
to improve performance or lower the costs of measurements. Alternate determinative
techniques, such as the substitution of spectroscopic or other techniques, and changes that
degrade method performance are not allowed. If an analytical technique other than the
techniques specified in this method is used, that technique must have a specificity equal to
or better than the specificity of the techniques in this method for the analyte(s) of interest.
9.1.2.1 Each time a modification is made to this method, the analyst is required to repeat
the procedure in Section 9.2. If the detection limit of the method will be affected
by the change, the laboratory is required to demonstrate that the MDL is lower
than one-third the regulatory compliance level or as low as or lower than that
listed in Section 1.3. If calibration will be affected by the change, the analyst
must recalibrate the instrument per Section 10.4.
9.1.2.2 The laboratory is required to maintain records of modifications made to this

method. These records include the information in this subsection, at a minimum.
9.1.2.2.1 The names, titles, addresses, and telephone numbers of the analyst(s)
who performed the analyses and modification, and of the quality
control officer who witnessed and will verify the analyses and modifi-
cation.
9.1.2.2.2 A narrative stating the reason(s) for the modification.
9.1.2.2.3 Results from all quality control (QC) tests comparing the modified
method to this method including:
a) calibration (Section 10.4)
b) calibration verification (Section 9.5)
c) initial precision and recovery (Section 9.2.2)
d) analysis of blanks (Section 9.4)

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e) ongoing precision and recovery (Section 9.6)
f) matrix spike and matrix spike duplicate (Section 9.3)
9.1.2.2.4 Data that will allow an independent reviewer to validate each determi-
nation by tracing the instrument output (peak height, area, or other
signal) to the final result. These data are to include:
a) sample numbers and other identifiers
b) analysis dates and times
c) analysis sequence/run chronology
d) sample weight or volume
e) sample volume prior to each cleanup step, if applicable
f) sample volume after each cleanup step, if applicable
g) final sample volume prior to injection
h) injection volume
i) dilution data, differentiating between dilution of a sample or

modified sample
j) instrument and operating conditions
k) other operating conditions
l) detector
m) printer tapes, disks, and other recording of raw data
n) quantitation reports, data system outputs, and other data necessary

to link raw data to the results reported
9.1.3 Analyses of MS/MSD samples are required to demonstrate method accuracy and precision
and to monitor matrix interferences (interferences caused by the sample matrix). The
procedure and QC criteria for spiking are described in Section 9.3.
9.1.4 Analyses of laboratory reagent blanks (LRBs) are required to demonstrate freedom from
contamination and that the compounds of interest and interfering compounds have not
been carried over from a previous analysis. The procedures and criteria for analysis of an
LRB are described in Section 9.4.
9.1.5 The laboratory shall, on an ongoing basis, demonstrate through the analysis of the LCS
that the analytical system is in control. This procedure is described in Section 9.6.

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9.1.6 The laboratory should maintain records to define the quality of data that is generated.
Development of accuracy statements is described in Sections 9.3.8 and 9.6.3.
9.1.7 Accompanying QC for the determination of cyanide is required per analytical batch. An
analytical batch is a set of samples analyzed at the same time to a maximum of
10 samples. Each analytical batch of 10 or fewer samples must be accompanied by a
laboratory reagent blank (LRB, Section 9.4), a laboratory control sample (LCS, Section
9.6), and a matrix spike and matrix spike duplicate (MS/MSD, Section 9.3), resulting in a
minimum of five analyses (1 sample, 1 LRB, 1 LCS, 1 MS, and 1 MSD) and a maximum
of 14 analyses (10 samples, 1 LRB, 1 LCS, 1 MS, and 1 MSD) in the batch. If more than
10 samples are analyzed at one time, the samples must be separated into analytical
batches of 10 or fewer samples.
9.2 Initial Demonstration of Laboratory Capability
9.2.1 Method Detection Limit (MDL)—T o establish the ability to detect cyanide at low levels,
the analyst shall determine the MDL per the procedure in 40 CFR 136, Appendix B
(Reference 15.2) using the apparatus, reagents, and standards that will be used in the
practice of this method. An MDL less than or equal to the MDL listed in Section 1.3 must
be achieved prior to practice of this method.
9.2.2 Initial Precision and Recovery (IPR)—T o establish the ability to generate acceptable
precision and accuracy, the analyst shall perform the following operations:
9.2.2.1 Analyze four samples of the LCS (Section 9.6) according to the procedure
beginning in Section 10.0.
9.2.2.2 Using the results of the set of the four analyses, compute the average percent
recovery (x) and the standard deviation of the percent recovery ( s) for cyanide.
Use Equation 3 for the calculation of the standard deviation of the percent
recovery (s).
EQUATION 3
(Sx)2
s = Sx2 – n
n–1
Where:
s = Standard deviation
n = Number of samples
x = Percent recovery in each sample

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9.2.2.3 Compare s and x with the precision and percent recovery acceptance criteria
specified in Section 13.0. If the value of s exceeds the precision limit or the value
of x falls outside the range for recovery , system performance is unacceptable and
the problem must be found and corrected before the analysis may continue.
9.3 Matrix Spike/Matrix Spike Duplicate (MS/MSD)—The laboratory shall spike, in duplicate, a
minimum of 10% of all samples (one sample in duplicate in each batch of 10 samples) from a
given sampling site.
9.3.1 The concentration of the spike in the sample shall be determined as follows:
9.3.1.1 If, as in compliance monitoring, the concentration of cyanide in the sample is

being checked against a regulatory concentration limit, the spiking level shall be
at that limit or at one to five times higher than the background concentration of
the sample (determined in Section 9.3.2), whichever concentration is higher .
9.3.1.2 If the concentration of cyanide in a sample is not being checked against a limit,
the spike shall be at the concentration of the LCS or at least four times greater
than the MDL.
9.3.2 Analyze one sample aliquot out of each set of 10 samples from each site or discharge
according to the procedure beginning in Section 10.0 to determine the background
concentration of cyanide.
9.3.2.1 If necessary, prepare a stock solution appropriate to produce a concentration

level in the sample at the regulatory compliance limit or at one to five times the
background concentration of cyanide (Section 9.3.1).
9.3.2.2 Spike two additional sample aliquots with the spiking solution (Section 9.3.2.1)
and analyze these aliquots to determine the concentration after spiking.
9.3.3 Calculate the percent recovery of cyanide in each aliquot using Equation 4.
EQUATION 4
P = A – B ´ 100
T
Where:
P = Percent recovery
A = Measured concentration of cyanide after spiking (Section 9.3.2.2)
B = Measured background concentration of cyanide (Section 9.3.2)
T = True concentration of the spike

16
9.3.4 Compare the recovery to the QC acceptance criteria in Section 13.0. If percent recovery is
outside of the acceptance criteria, and the recovery of the LCS in the ongoing precision
and recovery test (Section 9.6) for the analytical batch is within the acceptance criteria, an
interference is present. In this case, the result may not be reported for regulatory compli-
ance purposes.
9.3.5 If the results of both the MS/MSD and the LCS test fail the acceptance criteria, the analyti-
cal system is judged to be out of control. In this case, the problem shall be identified and
corrected, and the analytical batch must be reanalyzed.
9.3.6 Compute the relative percent difference (RPD) between the two spiked sample results
(Section 9.3.2.2, not between the two percent recoveries) using Equation 5.
EQUATION 5
RPD = |D1 – D2| ´ 100

(D1 + D2) / 2
Where:
RPD = Relative percent difference
D1 = Concentration of cyanide in the spiked sample
D2 = Concentration of cyanide in the spiked duplicate sample
9.3.7 If the RPD is greater than 10%, the analytical system is judged to be out of control, and
the problem must be immediately identified and corrected. The analytical batch must be
reanalyzed.
9.3.8 As part of the QC program for the laboratory , method precision and accuracy for samples
should be assessed and records should be maintained. After the analysis of five spiked
samples in which the recovery passes the test in Section 9.3.4, compute the average
percent recovery ( Pa) and the standard deviation of the percent recovery ( sp). Express the
accuracy assessment as a percent recovery interval from Pa–2sp to Pa+2sp. For example, if
Pa = 90% and sp = 10% for five analyses, the accuracy interval is expressed as 70–1 10%.
Update the accuracy assessment on a regular basis (e.g., after each 5–10 new accuracy
measurements).
9.4 Laboratory Reagent Blanks (LRB)—Laboratory reagent blanks are analyzed to demonstrate
freedom from contamination.
9.4.1 Analyze an LRB initially (i.e., with the tests in Section 9.2) and with each analytical batch.
The LRB must be subjected to the exact same procedural steps as a sample.

17
9.4.2 If cyanide is detected in the LRB at a concentration greater than the ML, analysis of
samples is halted until the source of contamination is eliminated and consequent analysis
of another LRB shows no evidence of contamination.
9.5 Calibration Verification—Verify calibration of the analytical equipment before and after each
analytical batch of 14 or fewer measurements. (The 14 measurements will normally be
10 samples, 1 LRB, 1 LCS, 1 MS, and 1 MSD). This can be accomplished by analyzing the
midrange calibration standard and verifying that it is within the QC acceptance criteria for recov-
ery in Section 13.0. (The concentration of the calibration verification depends on the calibration
range being used.) Failure to attain recoveries within the acceptance criteria requires recalibration
of the analytical system (Section 10.4).
9.6 Laboratory Control Sample (LCS)—T o demonstrate that the analytical system is in control and
acceptable precision and accuracy is being maintained with each analytical batch, the analyst
shall perform the following operations:
9.6.1 Analyze an LCS (Section 7.2.3.4) with each analytical batch according to the procedure in
Section 10.0.
9.6.2 If the precision and recovery for the LCS are within the acceptance criteria specified in
Section 13.0, analysis of the batch may continue. If, however , the concentration is not
within this range, the analytical process is not in control. In this event, correct the prob-
lem, repeat the LCS test, and reanalyze the batch.
9.6.3 The laboratory should add results that pass the specification in Section 9.6.2 to IPR and
previous LCS data and update QC charts to form a graphic representation of continued
laboratory performance. The laboratory should also develop a statement of laboratory
data quality for cyanide by calculating the average percent recovery (R) and the standard
deviation of the percent recovery ( sr). Express the accuracy as a recovery interval from
R–2sr to R+2sr. For example, if R = 95% and sr = 5%, the accuracy is 85–105%.
9.7 Reference Sample—To demonstrate that the analytical system is in control, the laboratory may
wish to periodically test an external reference sample, such as a Standard Reference Material
(SRM) available from the National Institute of Standards and Technology (NIST). Corrective
action should be taken if the measured concentration significantly differs from the stated
concentration.
10.0 Configuration and Start-up
10.1 Instrument Configuration
10.1.1 Configure the OI Analytical CNSolution 3000 Analyzer according to the Operator ’s
Manual and verify that each module is properly powered on.
10.1.2 Verify that the Available Cyanide, Method OIA-1677 Cartridge (Part #A001982 or
#A002654) is configured as illustrated in the flow diagram shown in Section 17.0.

18
10.1.3 Connect the appropriate pump tubes to the cartridge and to their appropriate reagent
containers according to the flow diagram.
10.2 Instrument Stabilization
10.2.1 Start the pump, allowing the reagents to flow through the entire system.
10.2.2 Verify that the flowcell of each detector is pur ged of all bubbles and that the flow is stable
and free from surging.
10.2.3 Load a 10 mg/L cyanide calibrant into the sampling valve and inject it into the FIA
system.
10.2.4 Continue to inject 10 mg/L cyanide calibrant until three successive peak heights or area
results are within 5% RSD, indicating that the electrode system is stabilized.
10.2.5 Following stabilization, inject the highest concentration calibration standard until three
successive peak heights or area results are within 5% RSD, indicating stabilization at the
top of the calibration range.
10.3 Baseline Verification
10.3.1 Create and save a Method in WinFLOW. Refer to the WinFLOW Operator’s Manual
(Reference 15.12) for help on creating a Method.
10.3.2 Create and save a Sample Table in WinFLOW that will be used to generate a calibration
curve using at least three calibrants that cover the full range of expected concentrations in
the samples to be analyzed. This Sample Table should also be used to analyze all neces-
sary QC samples as well as the analytical batch of samples to be analyzed. For help on
creating a Sample Table, refer to the WinFLOW Operator’s Manual (Reference 15.12).
10.3.3 Select Collect Data in the W inFLOW main window, enter the user ’s identification, select
the appropriate Method and Sample Table, and begin to collect baseline data. Very sharp
fluctuations in the baseline and/or consistent drifting are typically signs of bubbles in the
flowcell. The flowcell must be free of bubbles prior to beginning analysis.
10.4 Calibration and Standardization
10.4.1 Prepare a series of at least three working calibrants using the stock solutions (Section 7.3)
according to Equation 2, covering the desired analysis range.
10.4.2 Place the calibrants in the autosampler in order of increasing concentration. Each calibrant
should be analyzed according to the analytical procedures in Section 1 1.0. A calibration
curve will be calculated by the WinFLOW software.
10.4.3 Acceptance or control limits for the calibration results should be established using the
difference between the measured value of each calibrant and the corresponding “true”
concentration.

19
10.4.4 Each calibration curve should be verified by analysis of a Laboratory Control Sample
(LCS, Section 9.5). Using WinFLOW software, calibration, verification, and sample
analysis may be performed in one continuous analysis.
11.0 Procedure
11.1 Ligand Exchange Reagent Treatment
Note: When the ligand exchange reagents are added to the cyanide containing solution in the
specified proportions, up to 5 mg/L cyanide ion will be liberated from metal complexes of
intermediate stability. If higher concentrations of cyanide are present, increase the amount
of ligand exchange reagent added, or dilute the cyanide containing solution appropriately .
11.1.1 Adjust the pH of the sample, standard, or blank to approximately 12.
11.1.2 Add 50 µL of WAD Reagent A (Section 7.2.3.4) and 100 µL of WAD Reagent B (Section
7.2.3.5) to 100 mL of sample, standard, or blank. Mix well.
11.1.3 Analyze the treated samples within 2 hours of adding ligand exchange reagents.
11.2 Analysis
11.2.1 Place all reagents on-line and allow to pump at least 10–15 minutes. Verify that there are
no bubbles in the flowcell. Obtain a stable baseline and autozero the baseline before
beginning the analysis.
11.2.2 Load the sampler tray with calibrants, blanks, samples, and QC samples.
Note: The matrix of the working standards, blanks, and QC samples should match that
of the samples being analyzed.
11.2.3 Using the Method and Sample Table created for the analytical batch to be analyzed and
with the baseline verified to be stable, begin the analysis by selecting the “Fast Forward”
button on the left side of the Data Analysis window in WinFLOW. This will initiate the
sequential analysis of samples as defined in the Sample Table.
11.2.4 When analysis is complete, pump reagent water through the system for at least
10–15 minutes. Stop the pump, release the tension on all pump tubes, and power off the
system.
12.0 Data Analysis and Calculations
12.1 The calibration curve allows for accurate quantitation of the concentration in each sample.
12.2 WinFLOW software reports the concentration of each sample relative to the calibration curve.

20
13.0 Method Performance
Range: 2.0 µg/L–5.0 mg/L

Throughput: 48 samples/hour
Precision:
2.0 µg/L <2% RSD
5.0 mg/L <1% RSD
Method Detection Limit (MDL): 0.5 µg/L
14.0 Pollution Prevention and Waste Management
14.1 It is the laboratory’ s responsibility to comply with all federal, state, and local regulations govern-
ing waste management, particularly the hazardous waste identification rules and land-disposal
restrictions. In addition, it is the laboratory’ s responsibility to protect air , water, and land resources
by minimizing and controlling all releases from fume hoods and bench operations. Also, compli-
ance is required with any sewage discharge permits and regulations.
14.2 For further information on waste management, consult Section 13.6 of Less is Better: Laboratory
Chemical Management for Waste Reduction (Reference 15.7).
15.0 References
15.1 Wilmont, J.C.; Solujic, L.; Milosavljevic, E. B.; Hendrix, J.L.; Rader , W.S. Formation of Thiocyan-
ate During Removal of Sulfide as Lead Sulfide Prior to Cyanide Determination. Analyst 1996,
121, 799–801.
15.2 Code of Federal Regulations, Part 136, Appendix B, Title 40,1994.
15.3 Ingersol, D.; Harris, W.R.; Bomberger, D.C.; Coulson, D.M. Development and Evaluation Proce-
dures for the Analysis of Simple Cyanides, Total Cyanides, and Thiocyanate in Water and Waste
Water: 1983; EPA-600/4-83-054; Environmental Protection Agency, Environmental Monitoring
Systems Laboratory, U.S. Government Printing Of fice: Washington, DC, 1983.
15.4 Milosavljevic, E.B.; Solujic, L.; Hendrix, J.L. Environ. Sci. Technol. 1995, 29 (No. 2), 426–430.
15.5 Guide to Method Flexibility and Approval of EPA Water Methods. Available from the National
Technical Information Service (PB97-1 17766).
15.6 Handbook for Analytical Quality Control in Water and Wastewater Laboratories: 1979; EPA-600/
4-79-019; Environmental Protection Agency, Environmental Monitoring Systems Laboratory , U.S.
Government Printing Of fice: Washington, DC, 1979.
15.7 Less is Better: Laboratory Chemical Management for Waste Reduction. Available from the Ameri-
can Chemical Society, Department of Government Regulations and Science Policy , 1155 16th
Street, NW, Washington, DC 20036.

21
15.8 Sample Preparation. Methods for the Chemical Analysis of Water and Wastes; EPA/600/4-79-020;
Environmental Protection Agency, Environmental Monitoring Systems Laboratory , U.S. Govern-
ment Printing Of fice: Washington, DC, 1983.
15.9Report of the Draft Method OIA-1677 Interlaboratory Validation Study, March 1997. Available
from OI Analytical, Box 9010, College Station, TX 77842-9010.
15.10Report of the Draft Method OIA-1677 Single Laboratory Validation Study, November 1996.
Available from OI Analytical, Box 9010, College Station, TX 77842-9010.
15.11Standard Methods for the Examination of Water and Wastewater, 20th ed.; American Public
Health Association: Washington, D.C., 1998.
15.12WinFLOW Software and Operator ’s Manual (Part #A002877). Available from OI Analytical, P.O.
Box 9010, College Station, TX, 77842-9010.
16.0 Glossary of Definitions and Purposes
The definitions and purposes are specific to this method but have been conformed to common usage as
much as possible.
16.1 Units of weights and measures and their abbreviations
16.1.1 Symbols
°C degrees Celsius
% percent
± plus or minus
³ greater than or equal to
£ less than or equal to
16.1.2 Alphabetical characters
g gram
L liter
mg milligram
mg/L milligram per liter
µg microgram
µg/L microgram per liter
mL milliliter
ppm parts per million
ppb parts per billion
M molar solution
N normal solution

22
16.2 Definitions
16.2.1 Available cyanide (used interchangeably with weak acid dissociable (W AD) cyanide)
consists of cyanide ion (CN –), hydrogen cyanide in water (HCN(aq)), and the cayno-
complexes of zinc, copper , cadmium, mercury, nickel, and silver .
16.2.2 Initial Precision and Recovery (IPR)—Four aliquots of the LRB spiked with the analytes
of interest and used to establish the ability to generate acceptable precision and accuracy .
An IPR is performed the first time this method is used and any time the method or instru-
mentation is modified.
16.2.3 Laboratory Control Sample (LCS)—An aliquot of LRB to which a quantity of the analyte
of interest is added in the laboratory . The LCS is analyzed like a sample. Its purpose is to
determine whether the methodology is in control and whether the laboratory is capable of
making accurate and precise measurements.
16.2.4 Laboratory Reagent Blank (LRB)—An aliquot of reagent water and other blank matrix
that is treated like a sample, including exposure to all glassware, equipment, and reagents
that are used with other samples. The LRB is used to determine if the method analyte or
other interferences are present in the laboratory environment, reagents, or apparatus.
16.2.5 Matrix Spike/Matrix Spike Duplicate (MS/MSD)—An aliquot of an environmental sample

to which a quantity of the method analyte is added in the laboratory . The MS/MSD is
analyzed like a sample. Its purpose is to determine whether the sample matrix contributes
bias to the analytical results. The background concentration of the analyte in the sample
matrix must be determined in a separate aliquot, and the measured values in the MS/MSD
must be corrected for the background concentration.
16.2.6 Method Detection Limit (MDL)—The minimum concentration of a substance that can be
measured and reported with 99% confidence that the analyte concentration is greater than
zero.
16.2.7 Minimum Level (ML)—The level at which the entire analytical system will give a recog-
nizable signal and acceptable calibration point, taking into account method-specific
sample and injection volumes.
16.2.8 Ongoing Precision and Recovery (OPR)—See Section 16.2.2, “Laboratory Control
Sample.”

23
17.0 Figures
100 µg/L
}
50 µg/L
}
0 µg/L 2.0 µg/L
}
}
Figure 1. Calibration (2.0–100 µg/L)
5.0 mg/L
}
1.0 mg/L
0.50 mg/L
}
}
Figure 2. Calibration (0.50–5.0 mg/L)

24
Figure 3. Calibration Curve (2.0 µg/L–5.0 mg/L)
Figure 4. Calibration Results (2.0 µg/L–5.0 mg/L)

25
Hydrochloric Acid ( �R�E�D�/�R�E�D �)� � � � � � � � � � � � � � � WHT/
WHT)
Part #A002966
Sample In
To
(WHT/WHT)
Hydrochloric Acid
(�R�E�D�/�R�E�D�)�� Waste
To (GRN/GRN)
GAS DIFFUSION
Waste MODULE DETECTOR
PUMP
HIGH VALVE
To
30 Waste
LOW cm
SAMPLE TO
IN WASTE
Ampero-
200 metric
µL
CARRIER TO 50
IN TEST cm
(RED/RED)
(WHT/WHT)
CNSolution 3000
Sodium Hydroxide��
Legend
Plumbed Sample Loop

Empty Mixing Coil,
TFE 0.031" I.D.
Exterior Tubing,
Teflon® 0.020" I.D. Interior Port
Connections
Exterior Tubing,
TFE 0.031" I.D. Pump Tubes
Exterior Tubing, Flowcell

PVC 0.040" I.D.
Figure 5. Detailed Flow Diagram for Available Cyanide, Method OIA-1677 by SFA on a CNSolution 3000, Cartridge Part #A001982 or A002654
26
Figure 6. Precision at 2.0 µg/L (<2% RSD)
Figure 7. Precision at 5.0 mg/L (<1% RSD)

27
Figure 8. WinFLOW Method Editor—Detector Channel Settings
Figure 9. WinFLOW Method Editor—Flow Control Settings

28
Figure 10. WinFLOW Method Editor—Signal Filter and Marking Settings
Figure 11. WinFLOW Method Editor—Calibration and Quantitation Settings

29
Figure 12. WinFLOW Method Editor—Timed Events Editor
Figure 13. WinFLOW Method Editor—Calibrants Table Editor

30
18.0 Appendix
18.1 MDLs from nine laboratories were pooled to develop the MDL of 0.5 µg/L given in Section 1.3
(Reference 15.9).
18.2 Data obtained from single laboratory testing of the method are summarized in Table 1. Recoveries
and reproducibility for “free” forms of cyanide are shown, including the recovery and reproduc-
ibility of silver, nickel, mercurous, and mercuric cyanide species. Determination of these species
tends to be problematic with other methods for the determination of available cyanide. As it is the
case with other methods used for available cyanide, iron cyanide species were not recovered and
recoveries for gold and cobalt species were zero or very low . The complete results from the single
laboratory study are available in the Report of the Draft Method OIA-1677 Single Laboratory
Validation Study (Reference 15.10).
18.3 Listed in Table 2 are the QC acceptance criteria developed from an interlaboratory validation
study of this method. This study was conducted following procedures specified in the Guide to
Method Flexibility and Approval of USEPA Water Methods (Reference 15.5). A total of nine
laboratories performed analyses for various water matrices. Table 3 shows a summary of the
interlaboratory results, which include the accuracy and precision data as percent recoveries and
relative standard deviations. In addition to spikes of easily dissociable cyanides, some samples
contained known amounts of cyanides that are not recoverable (e.g., platinum and iron com-
plexes) and thiocyanate was spiked to one sample to investigate the potential for interference. The
complete study results are available in the Report of the Draft Method OIA-1677 Interlaboratory
Validation Study (Reference 15.9).
Table 1. Species-Dependent Cyanide Recoveries Using Method OIA-1677 1

Parameter Required Recovery Precision
Range (%)
Initial Precision and Recovery 92–122 < 5.1% RSD
Ongoing Precision and Recovery 82–132 n/a
Calibration Verification 86–118 n/a
1
Values are percent recoveries; numbers in parentheses are percent relative standard deviations.
Table 2. QC Acceptance Criteria

Species 0.20 mg/L CN– 2.0 mg/L CN–
[Zn(CN)4]2– 97.4 (0.7) 98.5 (0.7)
[Cd(CN)4]2– 100.0 (0.8) 100.0 (0.2)
[Cu(CN)4]2– 100.9 (1.3) 99.0 (0.6)
[Ag(CN)4]3– 101.8 (0.9) 100.0 (0.5)
[Ni(CN)4]2– 104.3 (0.2) 103.0 (0.5)
[Hg(CN)4]2– 100.0 (0.6) 99.0 (0.3)
Hg(CN)2 103.4 (0.4) 98.0 (0.3)
[Fe(CN)6]4– 0.0 (n/a) 0.0 (n/a)
[Fe(CN)6]3– 0.0 (n/a) 0.0 (n/a)

31
Table 3. Cyanide Recoveries From Various Aqueous Matrices

Sample Description Sample CN– Added CN– Average % Relative Standard
Concentration Concentration1 Recovery Deviation
Reagent Water w/0.01 M 0 µg/L 100 µg/L as KCN 108 4.0
Sodium Hydroxide
POTW Secondary Effluent 3.0 µg/L 100 µg/L as KCN, 102 7.0
2 mg/L as [Pt(CN)6]4–
Petroleum Refinery 9.9 µg/L 2 mg/L as KCN, 87 21
Secondary Effluent 5 mg/L as [Fe(CN)6]4–
Coke Plant Secondary 14.0 µg/L 50 µg/L as KCN 95 4.0
Effluent
Rolling Mill Direct Filter 4.0 µg/L none 80 41
Effluent
Metals Finishing Indirect 1.0 µg/L 200 µg/L as KCN, 92 16
Primary Effluent 2 mg/L as KSCN
Reagent Water w/0.01 M 0 µg/L 200 µg/L as KCN 101 8.0
Sodium Hydroxide
Reagent Water w/0.01 M 0 µg/L 10 mg/L as KCN, 103 2.0
Sodium Hydroxide 10 mg/L as [Pt(CN)6]4–
Mining Tailing Pond Effluent 842 µg/L 4 mg/L as KCN 98 3.0
1
Cyano-complexes of platinum and iron were added to the POTWand petroleum refinery effluents, respectively. Thiocyanate was added
to the metals finishing effluent to demonstrate that the FI/LE system does not determine these forms of cyanide.

32
Results were obtained under optimal operating conditions. Actual

results may vary depending on sample introduction, cleanliness of
sample containers, reagent purity , operator skill, and maintenance
of instruments.
Teflon is a registered trademark of E.I. du Pont de Nemours.

CNSolution is a trademark of OI Analytical.
WinFLOW is a trademark of OI Analytical.
P.O. Box 9010
College Station, Texas 77842-9010
Copyright 2001, OI Analytical, College Station, TX 77842. Tel: (979) 690-1711 · FAX: (979) 690-0440

33

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Method OIA-1677: Available Cyanide

Method OIA-1677: Available Cyanide by

1.0 Scope and Application

2.0 Summary of Method

Part #A002966 CNSolution 3000

Part #A002966 CNSolution 3000

5.3.1 Acetic Acid, glacial, C 2H4O2 (FW 60.05)

5.3.2 Acetone, C3H6O (FW 58.08)

5.3.3 5-[4-(Dimethylamino)benzylidene]rhodanine, C12H12N2OS 2 (FW 264.37)

5.3.4 Ethylenediamine, anhydrous, C 2H8N2 (FW 60.10)

5.3.5 Mercury(II) Cyanide, Hg(CN) 2 (FW 252.63)

5.3.6 Nickel(II) Cyanide, Ni(CN) 2 (FW 110.73)

5.3.7 Potassium Cyanide, KCN (FW 65.12)

5.3.8 Silver Nitrate, AgNO3 (FW 169.88)

5.3.9 Sodium Acetate, anhydrous, C 2H3O2Na (FW 82.03)

5.3.10 Sodium Hydroxide, NaOH (FW 40.00)

5.3.11 WAD Cyanide Reagent A (Part #A001416)

5.3.12 WAD Cyanide Reagent B (Part #A001417)

Part #A002966 CNSolution 3000

6.0 Apparatus, Equipment, and Supplies

6.1.1 120-Place Autosampler

6.1.2 Amperometric detection system with:

6.1.2.1 Silver working electrode

6.1.2.2 Silver/silver chloride reference electrode

6.1.2.3 Platinum/stainless steel counter electrode

6.1.2.4 Applied potential of zero volt

6.1.4 Available Cyanide, Method OIA-1677 Cartridge (Part #A001982 or #A002654)

7.0 Reagents and Calibrants

7.1 Raw Materials

7.1.1 Acetic Acid, glacial, C 2H4O2 (FW 60.05)

7.1.2 Acetone, C3H6O (FW 58.08)

7.1.3 Ascorbic Acid, C6H8O6 (FW 176.12)

7.1.4 Deionized Water (ASTM Type I or II)

7.1.5 5-[4-(Dimethylamino)benzylidene]rhodanine, C12H12N2OS 2 (FW 264.37)

7.1.6 Ethylenediamine, anhydrous, C 2H8N2 (FW 60.10)

7.1.7 Mercury(II) Cyanide, Hg(CN) 2 (FW 252.63)

7.1.8 Nickel(II) Cyanide, Ni(CN) 2 (FW 110.73)

Part #A002966 CNSolution 3000

7.1.9 Potassium Cyanide, KCN (FW 65.12)

7.1.10 Silver Nitrate, AgNO3 (FW 169.88)

7.1.11 Sodium Acetate, anhydrous, C 2H3O2Na (FW 82.03)

7.1.12 Sodium Hydroxide, NaOH (FW 40.00)

7.1.13 WAD Cyanide Reagent A (Part #A001416)

7.1.14 WAD Cyanide Reagent B (Part #A001417)

7.2 Reagent Preparation

7.2.1 Reagent Water

7.2.1.1.1 Place distilled/deionized water under a strong vacuum for

7.2.1.1.3 Boil distilled/deionized water in an Erlenmeyer flask for 15–20 minutes.

7.2.2 Sample Preservation Reagents

7.2.2.1 Acetate Buffer (1 L)

7.2.2.1.1 Dissolve 146 g of sodium acetate anhydrous in 400 mL of reagent

7.2.2.2 Ethylenediamine Solution, 3.5% v/v (100 mL)

7.2.2.2.1 Dilute 3.5 mL of ethylenediamine to 100 mL with reagent water in a

Part #A002966 CNSolution 3000

7.2.2.3 Ascorbic Acid—Crystals

7.2.3 Quality Control Reagents

7.2.3.1 Sodium Hydroxide, 1 M (1 L)

7.2.3.1.1 While stirring, carefully add 40 g of sodium hydroxide in 700 mL of

Warning: Mixing sodium hydroxide with water releases a great

Note: Store in an amber bottle at room temperature.

7.2.3.2.1 Dissolve 0.213 g of nickel(II) cyanide in 25 mL of reagent water and

7.2.3.2.2 Dilute to 100 mL with reagent water and mix well.

7.2.3.3.1 Dissolve 0.486 g of mercury(II) cyanide in 25 mL of reagent water and